CN103839622B - Halogen cross-linkable resin composition and insulated electric conductor, cable - Google Patents

Halogen cross-linkable resin composition and insulated electric conductor, cable Download PDF

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Publication number
CN103839622B
CN103839622B CN201310574464.9A CN201310574464A CN103839622B CN 103839622 B CN103839622 B CN 103839622B CN 201310574464 A CN201310574464 A CN 201310574464A CN 103839622 B CN103839622 B CN 103839622B
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ratio
base polymer
mass parts
mass
resin composition
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CN103839622A (en
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岩崎周
木村史
木村一史
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Proterial Ltd
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Hitachi Metals Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/446—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/448—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from other vinyl compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2962—Silane, silicone or siloxane in coating

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Insulated Conductors (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

The present invention provides has anti-flammability and superior mechanical properties, have high oil resistivity and superior low temperature characteristic simultaneously concurrently, Halogen cross-linkable resin composition, the insulated electric conductor being coated with this resin combination and cable (particularly vehicle is used) that die waste, electric wire/cable stick to each other can be prevented.This insulated electric conductor (1) has conductor (11a) and the insulating barrier (11b) being made up of Halogen cross-linkable resin composition formed in its periphery, said composition, relative to the base polymer of 100 mass parts, contains silicone rubber with the ratio of 0.5～10 mass parts, contains metal hydroxides with the ratio of 100～250 mass parts.Base polymer in said composition, as main constituent, with (a): the acid-modified polyolefin resin that glass transition temperature (Tg) is less than 55 DEG C that the ratio (mass ratio) of (b)=70:30～100:0 records based on DSC method containing (a) ethylene vinyl acetate copolymer (EVA) and (b), the vinyl acetate content (VA amount) of this base polymer is 50～70 mass % simultaneously.

Description

Halogen cross-linkable resin composition and insulated electric conductor, cable
Technical field
The present invention relates to the Halogen cross-linkable resin composition of a kind of anti-flammability, and be coated with the insulation of this resin combination Electric wire and cable (particularly vehicle insulated electric conductor and cable).
Background technology
More and more higher to the consciousness of environmental problem in the world, and when being seeking to burning, do not produce the what is called of halogen gas Halogen-free material in insulated electric conductor and cable.The exhausted of the halogen-free flame retardants such as metal hydroxides is employed for example, as it is known that have Edge electric wire (for example, with reference to patent documentation 1).
For the high flame retardant that flame can be suppressed when obtaining fire to propagate, need the such halogen-free flame retardants of a large amount of filling, If but fill in a large number, then there is mechanical property and reduce, melt fluidity also reduces simultaneously, and forming machine is restricted such asking Topic.
On the other hand, the insulated electric conductor in the vehicle such as rail truck, automobile and cable, according to the environment used, Need that there is high oil resistivity and low-temperature characteristics.
It is known as obtaining high oil resistivity, uses polymer that crystallinity is high or the high polymer of polarity preferably, additionally, be Obtain low-temperature characteristics, use the material that glass transition temperature (Tg) is low preferably.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-97881 publication
Summary of the invention
The problem that invention is to be solved
But, use, if obtaining high oil resistivity, the polymer that crystallinity is high, then flexible reduction, if being applied In insulated electric conductor and cable, then there is the such problem of routability deterioration.
Additionally, the polymer that polarity is high, such as vinyl acetate content (VA amount) are the vinyl acetate second of more than 50 mass % Enoate copolymer (EVA) although while flexibility when the temperature remains within the normal range oil resistivity the most excellent, but it is high to there is Tg, and low-temperature characteristics is poor Such problem.
And then, the VA high EVA of amount room temperature and melted time cementability high, when extrusion molding, material can be caused at mould Tool rollback around the phenomenon (hereinafter referred to as die waste (ダ イ ス カ ス)) accumulated.If die waste be attached to electric wire, The surface of cable, then can make degraded appearance.Further, VA measures high EVA and has adhesion, has the electric wire after molding, cable adhesion Problem.
The present invention proposes in view of the above problems, its object is to provide a kind of at the machine with anti-flammability and excellence While tool characteristic, have the low-temperature characteristics of high oil resistivity and excellence concurrently, and be prevented from die waste, electric wire sticks to each other Halogen cross-linkable resin composition, and be coated with the insulated electric conductor of this resin combination and cable (particularly vehicle insulation Electric wire and cable).
For the method solving problem
To achieve these goals, according to the present invention, it is provided that following Halogen cross-linkable resin composition and insulated electric conductor, electricity Cable.
[1] a kind of Halogen cross-linkable resin composition, it is characterised in that relative to the base polymer of 100 mass parts, with The ratio of 0.5～10 mass parts contains silicone rubber and contains metal hydroxides with the ratio of 100～250 mass parts；
Described base polymer, as main constituent, with (a): the ratio (mass ratio) of (b)=70:30～100:0 contains (a) The glass transition temperature (Tg) that ethylene vinyl acetate copolymer (EVA) and (b) record based on DSC method is less than-55 DEG C Acid-modified polyolefin resin, meanwhile, the vinyl acetate content (VA amount) of this base polymer is 50～70 mass %.
[2] the Halogen cross-linkable resin composition as described in above-mentioned [1], it is characterised in that described EVA is by melt flow rate (MFR) (MFR) different two or more EVA is constituted, meanwhile, containing the EVA that MFR is more than 15g/10min of 5～20 mass %.
[3] a kind of insulated electric conductor, it is characterised in that be coated with the Halogen crosslinked resin group described in above-mentioned [1] or above-mentioned [2] Compound is as insulating barrier.
[4] a kind of cable, it is characterised in that there is the insulated electric conductor described in above-mentioned [3].
[5] a kind of cable, it is characterised in that be coated with the Halogen cross-linkable resin composition described in above-mentioned [1] or above-mentioned [2] As sheath.
Invention effect
According to the present invention, it is possible to provide while a kind of mechanical property possessing anti-flammability and excellence, have concurrently high oil resistivity and Excellent low-temperature characteristics, and be prevented from die waste, Halogen cross-linkable resin composition that electric wire/cable sticks to each other, and It is coated with insulated electric conductor and the cable (particularly vehicle insulated electric conductor and cable) of this resin combination.
Accompanying drawing explanation
Fig. 1 is the sectional view of an embodiment of the insulated electric conductor representing the present invention.
Fig. 2 is the sectional view of an embodiment of the cable representing the present invention.
Description of reference numerals
11: insulated electric conductor；11a: conductor；11b: insulating barrier；12: cable；12a: conductor；12b: insulating barrier；12c: sheath
Detailed description of the invention
Hereinafter, referring to the drawings the insulated electric conductor of the present invention and an embodiment of cable are specifically described.
(insulated electric conductor)
Fig. 1 is the sectional view of an embodiment of the insulated electric conductor representing the present invention.
As it is shown in figure 1, the insulated electric conductor 11 involved by present embodiment has by structures such as general material such as tin-coated coppers The conductor 11a become and the insulating barrier 11b formed in the periphery of conductor 11a.
Insulating barrier 11b is made up of Halogen cross-linkable resin composition, and described Halogen cross-linkable resin composition is relative to 100 mass The base polymer of part, contains silicone rubber with the ratio of 0.5～10 mass parts and contains with the ratio of 100～250 mass parts Metal hydroxides.
Base polymer in Halogen cross-linkable resin composition, as main constituent, with (a): (b)=70:30's～100:0 The glass transition temperature that ratio (mass ratio) records based on DSC method containing (a) ethylene vinyl acetate copolymer (EVA) and (b) Degree (Tg) is the acid-modified polyolefin resin of less than-55 DEG C, and meanwhile, the vinyl acetate content (VA amount) of this base polymer is 50～70 mass %.
Usually, the kind for the polymer of base polymer has 1,2,3 ... k ... when n, in base polymer VA amount by following formula (1) derive.That is,
[mathematical expression 1]
In above-mentioned formula (1), X represents polymerkVA amount (quality %), Y represents polymerkAccount for the ratio that base polymer is overall Example, and k represents natural number.
In the present embodiment, if the VA amount of the base polymer of the Halogen cross-linkable resin composition used is less than 50 matter Amount %, then can not meet oil resistivity；If more than 70 mass %, then can not obtain low-temperature characteristics.Additionally, EVA burning time occur by The heat absorption that desacetoxy causes.Therefore, if VA amount is low, then there is the tendency that anti-flammability reduces.
In the present embodiment, based on, (a) EVA of one of constituent of polymer is by melt flow rate (MFR) (MFR) different two or more compositions, likewise it is preferred that the EVA that MFR is more than 15g/10min containing 5～20 mass %.More excellent Elect 5～15 mass %, more preferably 5～10 mass % as.Its reason is because by being set in by the EVA content of high MFR In the range of Gai, it is possible to increase melt fluidity and productivity.That is, if the MFR of all EVA used is respectively less than 15g/10min, Then output during extrusion molding, can reduce, and productivity reduces sometimes.If the EVA that MFR is more than 15g/10min is less than 5 matter Amount %, then output during extrusion molding, can reduce, and productivity reduces sometimes.If more than 20 mass %, then at resin combination Time melted, adhesion is violent, takes out and become difficulty sometimes in the batch-type mixer such as kneader.Additionally, be 15g/ about MFR VA amount in the EVA of more than 10min is not particularly limited, as long as the VA amount making base polymer overall is that 50～70 mass % are Can.
And then, based on the content of (b) acid-modified polyolefin resin of another constituent of polymer, with (a) In the mass ratio of ethylene vinyl acetate copolymer (EVA), if ratio (a): (b)=70:30～100:0 is big (more than 30 mass %), Then oil resistivity reduces.It is preferably (a): the ratio of (b)=70:30～90:10.More preferably (a): (b)=80:20's～90:10 Ratio.If additionally, use Tg than-55 DEG C of high (b) acid modified polyolefins, then low-temperature characteristics reduces.It is less than-55 DEG C as Tg Acid-modified polyolefin resin, be not particularly limited, but crystallinity low in the case of flexible good, be preferably fusing point 90 as target Acid-modified polyolefin resin below DEG C.Specifically, can enumerate and implement the modified ultra-low density polyethylene of acid, ethylene-propylene Acid methyl terpolymer, ethylene-ethyl acrylate copolymer, Ethylene/Butylene-1 copolymer, polyethylene-hexene-1 copolymer, ethylene- Octene-1 copolymer etc..Further, it is also possible to by these polymer and use.Additionally, due to by making itself and metal hydroxides Adaptation becomes well can improve low-temperature characteristics, and it is effective for therefore carrying out acid modification.As acid, maleic acid, Malaysia can be enumerated Anhydride, fumaric acid etc..
In the present embodiment, as long as playing this effect, it is also possible to containing except (a) vinyl acetate in base polymer Component of polymer beyond vinyl ester copolymers (EVA) and (b) acid-modified polyolefin resin.
In the present embodiment, as the silicone rubber of one of the substance in base polymer, if its addition is little In 0.5 mass parts, then produce die waste and there is the adhesion each other of electric wire, cable；If more than 10 mass parts, then tensile strength Reduce.Relative to the base polymer of 100 mass parts, preferably contain silicone rubber, more preferably with the ratio of 0.5～7.5 mass parts Silicone rubber is contained with the ratio of 0.5～5 mass parts.
Silicone rubber used in present embodiment, can enumerate dimethyl polysiloxane, methylvinyl-polysiloxane, first Base phenyl polysiloxane etc..Owing to the intermiscibility of silicone rubber Yu EVA is poor, the skin section of material can be transferred to after mixing, therefore It is prevented from die waste and electric wire adhesion each other.
Crosslinking method used in present embodiment has the chemical crosslinking utilizing organic peroxide or sulphur compound；Profit Cross-link with the irradiation of electron ray, lonizing radiation etc.；Utilizing the crosslinking etc. of other chemical reactions, any cross-linking method is the most applicable.
In the present embodiment, as the metal hydroxides of another substance in base polymer, if it contains Amount less than 100 mass parts, then can not obtain sufficient anti-flammability；If more than 250 mass parts, then cannot ensure low-temperature characteristics.Phase For the base polymer of 100 mass parts, preferably contain metal hydroxides with the ratio of 100～200 mass parts, more preferably with The ratio of 100～150 mass parts contains hydroxide.
As the metal hydroxides used in present embodiment, can enumerate such as aluminium hydroxide, magnesium hydroxide, hydroxide Calcium etc..The calcium hydroxide caloric receptivity when decomposing is about 1000J/g, on the other hand, due to aluminium hydroxide, the heat absorption of magnesium hydroxide Amount up to 1500～1600J/g, anti-flammability is good, the most preferably.In view of dispersibility etc., silane coupler, titanium can be passed through Fire retardant is implemented surface and is processed by the fatty acids such as acid esters system coupling agent, stearic acid etc..
In the Halogen cross-linkable resin composition being made up of these materials, as required, crosslinking coagent, fire-retardant can be added Auxiliary agent, UV absorbent, light stabilizer, softening agent, lubricant, coloring agent, reinforcing agent, surfactant, inorganic filler, Plasticizer, metal-chelator, foaming agent, compatilizer, processing aid, stabilizer etc..
Additionally, in the present embodiment, insulating barrier can be constituted with monolayer, in addition it is also possible to form multiple structure.As Form concrete example during multiple structure, can enumerate and be coated with above-mentioned Halogen cross-linkable resin composition in outermost layer extrusion, and, Structure obtained by extrusion is coated with vistanex beyond outermost layer.As vistanex, can enumerate Low Density Polyethylene, EVA, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate ethylene oxidic ester copolymerization Thing, maleic anhydride polyolefin etc., these can be used alone, or two or more is used in mixed way.And then, as required, it is also possible to Implement separation, combination etc..
The material used as the insulating barrier beyond outermost layer, it is possible to be suitable for elastomeric material, ethylene-propylene can be enumerated Copolymer rubber (EPR), ethylene-propylene-diene terpolymer rubber (EPDM), acrylonitrile-butadiene rubber (NBR), hydrogen Change NBR(HNBR), acrylic rubber, vinyl-acrylate copolymer rubber, POE rubber (EOR), ethylene- Vinyl acetate copolymer rubber, Ethylene/Butylene-1 copolymer rubber (EBR), butadienestyrene copolymer rubber (SBR), Isobutylene-isoprene copolymer rubber (IIR), there is the block copolymer rubber of polystyrene block, polyurethane rubber, phosphorus Nitrile rubbers etc., these can be used alone or two or more are used in mixed way.
Additionally, be not limited to said polyolefins resin, elastomeric material, as long as having insulating properties, it is not particularly limited.Root According to needs, it is also possible to add fire retardant, flame retardant, cross-linking agent, crosslinking coagent, UV absorbent, light stabilizer, softening Agent, lubricant, coloring agent, reinforcing agent, surfactant, antioxidant, inorganic filler, coupling agent, plasticizer, metal-chelating Agent, foaming agent, compatilizer, processing aid, stabilizer etc..Crosslinking Treatment has the chemistry utilizing organic peroxide or sulphur compound Crosslinking；The irradiation utilizing electron ray, lonizing radiation etc. cross-links；Utilizing the crosslinking etc. of other chemical reactions, any cross-linking method is equal Applicable.
(cable)
Fig. 2 is the sectional view of an embodiment of the cable representing the present invention.
As in figure 2 it is shown, the cable 12 involved by present embodiment has by leading that versatile material such as tin-coated copper etc. is constituted Body 12a, the insulating barrier 12b formed in the periphery of conductor 12a and the sheath 12c formed in the periphery of insulating barrier 12b.
Insulating barrier 12b is by such as from Ethylene/Butylene-1 copolymer rubber, PBN, poly-terephthaldehyde More than one the polymer selected in the group of acid butanediol ester, polyphenylene oxide and polyether-ether-ketone composition is constituted.Can also be by above-mentioned Halogen cross-linkable resin composition is formed.
Sheath 12c is formed by above-mentioned Halogen cross-linkable resin composition.
Further, about the details of Halogen cross-linkable resin composition, due to identical with during above-mentioned insulated electric conductor, therefore The description thereof will be omitted.
Additionally, in the present embodiment, sheath can be constituted with monolayer, in addition it is also possible to form multiple structure.As shape Become concrete example during multiple structure, can enumerate and be coated with above-mentioned Halogen cross-linkable resin composition in outermost layer extrusion, and, Structure obtained by extrusion is coated with vistanex beyond outer layer.As vistanex, can enumerate Low Density Polyethylene, EVA, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate ethylene oxidic ester copolymerization Thing, maleic anhydride polyolefin etc., these can be used alone, or two or more is used in mixed way.And then, as required, it is also possible to Implement separation, combination etc..
(Halogen cross-linkable resin composition)
Halogen cross-linkable resin composition involved by embodiments of the present invention, relative to the base polymer of 100 mass parts Thing, contains silicone rubber with the ratio of 0.5～10 mass parts and contains metal hydroxides with the ratio of 100～250 mass parts； Described base polymer, as main constituent, with (a): the ratio (mass ratio) of (b)=70:30～100:0 contains (a) vinyl acetate The acid that the glass transition temperature (Tg) that vinyl ester copolymers (EVA) and (b) record based on DSC method is less than-55 DEG C is modified poly- Olefin resin, meanwhile, the vinyl acetate content (VA amount) of this base polymer is 50～70 mass %.About Halogen crosslinking tree The details of oil/fat composition, as previously mentioned.
Halogen cross-linkable resin composition involved by embodiments of the present invention may be used for various uses, but due at tool While having the mechanical property of anti-flammability and excellence, have the low-temperature characteristics of high oil resistivity and excellence concurrently, it is possible to prevent die waste, Electric wire/cable adhesion each other, is therefore applicable to the sheath of the insulating barrier of insulated electric conductor, cable.Especially, it is applicable to car With insulated electric conductor and car cable.
Embodiment
Below, use embodiment that the cable of the present invention is specifically described further.Further, the present invention is not by following reality Execute any restriction of example.
(embodiment 1)
Cable shown in manufacture Fig. 2 as follows.That is, as conductor, the tin-coated copper using structure to be 80/0.40mm is led Body；As insulating barrier, use Ethylene/Butylene-1 copolymer rubber (Mitsui Chemicals, Inc.'s system, commodity relative to 100 mass parts Name: Toughmer A-4050S) add 2 mass parts organic peroxides (Nof Corp.'s system, trade name: PERBUTYL P) The resin combination of (PERBUTYL is registered trade mark)；As sheath, use as shown in Table 1 join what suitable materials was constituted Halogen cross-linkable resin composition.With 4.5 inches of crosslinked extrused machines of continuous steam, these resin combinations are carried out bilayer be expressed into The periphery of conductor so that the thickness of insulating barrier is 0.45mm, and the thickness of sheath is 1.67mm, is overmolding to external diameter 8.60mm. Crosslinking uses the high steam of 1.8MPa to carry out 3 minutes, obtains cable.Further, the EVA of 1～3 in table 1 is that MFR is less than 15g/ The EVA of 10min.
Now, as the material of the Halogen cross-linkable resin composition constituting sheath, use and be respectively cooperating with 100 mass parts EVA(VA:60 mass %) (LANXESS system, trade name: Levapren600) (Levapren is registered trade mark), the silicon of 5 mass parts Rubber (dimethyl polysiloxane, chemical company of SHIN-ETSU HANTOTAI system, trade name: KE76), organic peroxide (Japan's oil of 2 mass parts Fat company system, trade name: PERBUTYL P) (PERBUTYL is registered trade mark), magnesium hydroxide (the consonance chemistry of 100 mass parts Company's system, trade name: Kisuma5L) the Halogen cross-linkable resin composition of (Kisuma is registered trade mark).
Further, by using the insulation joining the Halogen cross-linkable resin composition formation that suitable materials is constituted as shown in Table 1 Layer replaces the sheath in the cable shown in Fig. 2, has manufactured the insulation involved by the embodiments of the present invention shown in Fig. 1 equally Electric wire.Evaluation result is to play the effect of the present invention.
To the cable obtained, especially by various evaluation tests shown below required in rail truck purposes It is evaluated.Its evaluation result is shown in Table 1.
[evaluation test]
(evaluation of mixed refining process)
The suitable materials 25L kneader of joining of the sheath shown in table 1 is carried out mixing, by self design temperature 50 DEG C After heating raises the temperature to 150 DEG C, tilting material room, the situation that material falls naturally is set to ◎, can be fallen by hands operation Situation is set to zero, and situation about can not doing out completely is set to ×.
(evaluation of extrusion)
On cable when coated insulation layer and sheath, squeeze if implementing bilayer with 4.5 inches of crosslinked extrused machines of continuous steam The highest hauling speed when going out is that more than 20m/min is then set to ◎, is then set to less than 20m/min if 1m/min Zero, be set to during entirely without traction ×.
(evaluation of die waste)
On cable when coated insulation layer and sheath, real with 4.5 inches of crosslinked extrused machines of continuous steam by visualization The mould after extrusion 100m when executing double-deck extrusion, confirms with or without die waste.If there being die waste, be set to ×, if do not had Die waste is had then to be set to ◎.
(evaluation of adhesion)
On cable when coated insulation layer and sheath, when implementing bilayer extrusion with 4.5 inches of crosslinked extrused machines of continuous steam Extrusion 100m after, be wound up on the bobbin of diameter 450mm, after 60 minutes during manipulated untwisted cable, if cable sticks to each other, be set to ×, can untie well without adhesion, be set to ◎.
(evaluation of anti-flammability)
Implement the Vertical Flame Test according to EN60332-1-2.The cable of vertical support 550mm, from top The position contact flame of 475mm 60 seconds, after taking off, if ember self fire extinguishing in the range of 50mm～540mm from top Then it is set to ◎；Be set to when ember is beyond above-mentioned scope ×.
(evaluation of sheath)
The evaluation of sheath is cutting insulating barrier, and sheath section is made into No. 6 dumb-bell test pieces, implements tests below.
Tensile strength is evaluated
According to EN60811-1-1, under draw speed 200mm/min, implement tension test.Tensile strength is more than 10MPa Situation be set to ◎；Situation less than 10MPa is set to ×.
Oil resistivity is evaluated
According to EN60811-2-1, it is impregnated into and is heated in the test oil IRM903 of 70 DEG C, after 168 hours, to implement stretching examination Test.Elongation change be less than 40% situation be set to ◎；Situation more than 40% is set to ×.
Low-temperature characteristics is evaluated
According to EN60811-1-4, it is set to ◎-40 DEG C of situations showing more than 30% percentage elongation；Percentage elongation is less than 30% Time be set to ×.
(overall merit)
As overall merit, all evaluations are the situation of ◎ and are set to excellent (◎), evaluate situation about being made up of ◎ and zero Be set to good (zero), though have in arbitrarily evaluating one defective (×) be defective (×).
Table 1
(embodiment 2～14)
In embodiment 1, by the material shown in the embodiment that cooperation material altering is table 1 2～14 of sheath, except this with The outer cable manufacturing embodiment 2～14 similarly to Example 1.
Similarly to Example 1 the cable obtained is evaluated by various evaluation tests.Its evaluation result is shown in In table 1.
As shown in table 1, in the case of embodiment 1～4, extrusion processability is zero, and overall merit is zero.
The mixed refining process of embodiment 9 and 11, and the extrusion processability of embodiment 12 and 14 is zero, embodiment 9,11, The overall merit of 12 and 14 is zero.
In the case of embodiment 5～8,10 and 13, all evaluations are ◎, and overall merit is ◎.
(comparative example 1～8)
In embodiment 1, it is the material shown in table 2 by the cooperation material altering of sheath, same with embodiment 1 in addition Sample ground manufactures the cable of comparative example 1～8.
Similarly to Example 1 the cable obtained is evaluated by various evaluation tests.Its evaluation result is shown in In table 2.
Table 2
As shown in table 2, in the case of comparative example 1, the VA content of base polymer is low, and anti-flammability, oil resistivity be ×.Cause This, overall merit is ×.
In the case of comparative example 2, the VA content of base polymer is high, and low-temperature characteristics is ×.Therefore, overall merit be ×.
In the case of comparative example 3, the addition of acid modified polyolefin is too much, and oil resistivity is ×.Therefore, overall merit is ×。
In the case of comparative example 4, the Tg of acid modified polyolefin is high, and low-temperature characteristics is ×.Therefore, overall merit be ×.
In the case of comparative example 5, the addition of magnesium hydroxide is low, and anti-flammability is ×.Therefore, overall merit be ×.
In the case of comparative example 6, the addition of magnesium hydroxide is many, and low-temperature characteristics is ×.Therefore, overall merit be ×.
In the case of comparative example 7, owing to not adding silicone rubber, therefore die waste occurs, cable also stickness.Therefore, Overall merit is ×.
In the case of comparative example 8, owing to the addition of silicone rubber is many, therefore tensile strength reduces.Therefore, overall merit is ×。

Claims (4)

1. a rail truck insulated electric conductor, it is characterised in that be coated with Halogen cross-linkable resin composition as insulating barrier, institute State the Halogen cross-linkable resin composition base polymer relative to 100 mass parts, contain silicon rubber with the ratio of 0.5～10 mass parts Glue and contain metal hydroxides with the ratio of 100～250 mass parts；
Described base polymer, as main constituent, with (a): the mass ratio of (b)=70:30～90:10 contains (a) vinyl acetate The acid that the glass transition temperature (Tg) that vinyl ester copolymers (EVA) and (b) record based on DSC method is less than-55 DEG C is modified poly- Olefin resin, meanwhile, the vinyl acetate content (VA amount) of this base polymer is 50～70 mass %.
2. rail truck insulated electric conductor as claimed in claim 1, it is characterised in that described ethylene vinyl acetate copolymer The two or more ethylene vinyl acetate copolymer different by melt flow rate (MFR) (MFR) is constituted, meanwhile, containing 5～20 matter The ethylene vinyl acetate copolymer that melt flow rate (MFR) is more than 15g/10min of amount %.
3. a rail truck cable, it is characterised in that have rail truck insulated electric conductor, described insulated electric conductor is coated with Halogen cross-linkable resin composition is as insulating barrier, and described Halogen cross-linkable resin composition is relative to the base polymer of 100 mass parts Thing, contains silicone rubber with the ratio of 0.5～10 mass parts and contains metal hydroxides with the ratio of 100～250 mass parts；
Described base polymer, as main constituent, with (a): the mass ratio of (b)=70:30～90:10 contains (a) vinyl acetate The acid that the glass transition temperature (Tg) that vinyl ester copolymers (EVA) and (b) record based on DSC method is less than-55 DEG C is modified poly- Olefin resin, meanwhile, the vinyl acetate content (VA amount) of this base polymer is 50～70 mass %.
4. a rail truck cable, it is characterised in that be coated with Halogen cross-linkable resin composition as sheath, described Halogen Cross-linkable resin composition relative to the base polymer of 100 mass parts, with the ratio of 0.5～10 mass parts contain silicone rubber and Metal hydroxides is contained with the ratio of 100～250 mass parts；
Described base polymer, as main constituent, with (a): the mass ratio of (b)=70:30～90:10 contains (a) vinyl acetate The acid that the glass transition temperature (Tg) that vinyl ester copolymers (EVA) and (b) record based on DSC method is less than-55 DEG C is modified poly- Olefin resin, meanwhile, the vinyl acetate content (VA amount) of this base polymer is 50～70 mass %.
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